Patent GB-354716-A (GB)
Title: Process for the manufacture of vat dyestuffs
IPC: C09B7/00
Filed: 1930-05-09
Abstract: Anthraquinonyl derivatives of indigoid amides.-Vat dyes are obtained by condensing an isatin-Bz-carboxylic acid or nuclear substitution product thereof with hydroxythionaphthenes, indoxyls or nuclear substitution products thereof, and the dyestuff acids reacted with aminoanthraquinones or nuclear substitution products thereof in the customary manner.  Alternatively an isatin-Bz-carboxylic acid is first reacted with an amino-anthraquinone or nuclear substitution product thereof and the intermediate product so obtained condensed with hydroxythionaphthenes, indoxyls or nuclear substitution products thereof.  The carboxylic acids may be first transformed into acid halides or other reactive derivatives prior to condensation as set forth in these two processes.  Further similar dyestuffs are obtained by condensing a hydroxythionaphthene-Bz-carboxylic acid or reactive a -derivative with the components customarily used for preparing indigoid dyestuffs and reacting these dyestuff acids with aminoanthraquinones.  The coupling components include, for example, cyclic o-diketones or cyclic compounds containing a reactive-COCH2-group, or reactive a -derivatives thereof, or alternatively the hydroxythionaphthene-Bz-carboxylic acid may be oxidized, for example with potassium ferricyanide or air in the p presence of copper salts, to give thioindigos containing two substituent carboxylic acid groups.  Also included in such coupling components are the isatin-Bz-carboxylic acids whereby dicarboxylic acid derivatives are again obtained.  The products surpass the known indirubin dyestuffs in their tinctorial properties, being easily vatted and yielding fast, clear dyeings; they are also suitable for calico printing.  According to examples or tables dyestuffs are prepared as follows: (1) Isatin-7-carboxylic acid is (i) condensed with 5-chloro-hydroxythionaphthene, the product converted to the acid chloride, and condensed with a -amino-anthraquinone (dyes yellow-red); or b -amino-anthraquinone may be used instead (dyes red); (ii) condensed with 4 : 5-benzo-hydroxythionaphthene, the product converted to the acid chloride and condensed with a -aminoanthraquinone (dyes reddish-brown); or the same product is obtained by condensing isatin-7-carboxylic acid chloride with a -aminoanthraquinone (which dyes light-yellow) and this derivative with 4 : 5-benzo-hydroxythionaphthene; (iii) condensed with 4-methyl-6-chlorohydroxythionaphthene, the product converted to the acid chloride and condensed with b -aminoanthraquinone (dyes scarlet-red); (iv) condensed with 6-ethoxyhydroxythionaphthene and a -aminoanthraquinone (dyes yellowish-orange); (v) condensed with 6-ethoxyhydroxythionaphthene and 1-amino-5-benzoylaminoanthraquinone (yellowish - orange); (vi) condensed with 6-methoxy-hydroxythionaphthene and a -aminoanthraquinone (yellowish - orange) or b  - aminoanthraquinone (orange-yellow); (vii) condensed with 4,6-dimethylhydroxythionaphthene and 1-amino-5-benzoylaminoanthraquinone (reddish-orange) or 1-amino-4-benzoylaminoanthraquinone (red); (viii) condensed with 4-methyl-6-chlorohydroxythionaphthene and a -aminoanthraquinone (reddish-orange); (ix) condensed with 5,6,7-trichlorohydroxythionaphthene and 1 - amino - 5 - benzoylamino-anthraquinone (reddish-orange); (x) condensed with 4-7-dimethyl-5-chlorohydroxythionaphthene and 1-amino-5-benzoylaminoanthraquinone (brownish-red) or a -aminoanthraquinone (red); (xi) condensed with Bz4-chloro-6,7-benzo-hydroxythionaphthene (Specification 222, 120, [Class 2 (iii), Dyes &c.]) and 1-amino-5-benzoylaminoanthraquinone (yellowish-brown); (xii) condensed with 5,6 - benzo - 7-chlorohydroxythionaphthene and a -aminoanthraquinone (Bordeaux); (xiii) is converted to the acid chloride, condensed with 1-amino-5-benzoylaminoanthraquinone (which dyes golden-yellow) and this product condensed with diacetyl-5 : 7-dichloroindoxyl (reddish-brown).  (2) Isatin-5-carboxylic acid is condensed with 6-methoxyhydroxythionaphthene, the product converted to the acid chloride, and condensed with a -aminoanthraquinone (yellowish-orange).  (3) 5-Chloroisatin-7-carboxylic acid is condensed (i) with 5-chlorohydroxythionaphthene and the acid chloride of the product with 1-amino-5-benzoylaminoanthraquinone (orange-red); (ii) with 5-bromohydroxythionaphthene and a -aminoanthraquinone (red).  (4) Hydroxythionaphthene-6-carboxylic acid is (i) oxidized with potassium ferricyanide to thioindigo-6-61-dicarboxylic acid and the acid chloride of the latter condensed with 1-amino-5-benzoylaminoanthraquinone (2 mols) (brown); (ii) condensed with acenaphthenequinone and the acid chloride of the product condensed with 1-amino-4-benzoylaminoanthraquinone (scarlet-red); (iii) condensed with 1-chloro-2,3-naphthisatin and the acid chloride of the product with 1-amino-4-benzoylaminoanthraquinone (reddish-brown); or 1-amino-5-benzoylaminoanthraquinone may be used (brown); (iv) condensed with a reactive a -derivative of 1-chloro-2,3-naphthisatin and 1-amino-4-benzoylaminoanthraquinone (bluish-black), or 1-amino-5-benzoylaminoanthraquinone (green); (v) condensed with monobromo - 2,1 - naphthisatin chloride and the acid chloride of the product with 1-amino-4-benzoylaminoanthraquinone (black), or 1-amino-5-benzoylaminoanthraquinone (olive-green); (vi) condensed with the dimethylaminoanil of 6-methoxyhydroxythionaphthene and the acid chloride of the product with 1-amino-4-benzoyl-aminoanthraquinone (red); or 1-amino-5-benzoyl-aminoanthraquinone may be used (reddish-orange), or 1-amino-4-methoxyanthraquinone (red); (vii) condensed with Bz4-chloro-6,7-benzohydroxythionaphthene and 1-amino-4-benzoylaminoanthraquinone (reddish-brown), or 1-amino-5-benzoyl-aminoanthraquinone (anthracene-brown); (viii) condensed with 5,7-dichlorisatin and a -aminoanthraquinone (reddish-brown), or 1-amino-4-benzoylaminoanthraquinone (copper red), or 1-amino - 5 - benzoylaminoanthraquinone (brownish red), or 1-amino-4-methoxyanthraquinone (reddish-brown); (ix) condensed with isatin-7-carboxylic acid and 2 mols of a -aminoanthraquinone (reddish-brown), or b -aminoanthraquinone (red), or 1-amino-4-benzoylaminoanthraquinone (copper red), or 1-amino-5-benzoylaminoanthraquinone (brown).  (5) Hydroxythionaphthene-7-carboxylic acid is (i) oxidized with potassium ferricyanide to thioindigo-7,71-dicarboxylic acid and the diacid chloride derived from the latter condensed with 1-amino-4-benzoylaminoanthraquinone (red); (ii) condensed with acenaphthenequinone and the acid chloride of this product with 1-amino-4-benzoylaminoanthraquinone (red); condensed with the dimethyl-aminoanil of 4-methyl-6-chlorohydroxythionaphthene, and the acid chloride with a -aminoanthraquinone (red).  Isatin-Bz-carboxylic acids may be prepared by Sandmeyer's process by treating an arylamino-carboxylic acid with a hydroxylamine salt and chloral hydrate and warming the product with concentrated sulphuric acid; thus isatin-7- and 5-carboxylic acids are prepared from o- and p-aminobenzoic acids respectively. 5-Chloroisatin-7-carboxylic acid is prepared bychlorinating the isatin-7-carboxylic acid in chlorobenzene by means of sulphuryl chloride. Hydroxythionaphthene-Bz-carboxylic acids are prepared from carboxylated phenylthioglycollic-o-carboxylic acids by ring closure in the customary manner; thus hydroxythionaphthene-6-carboxylic acid is prepared by ring-closing 2,5-dicarboxyphenyl-1-thioglycollic acid by means of acetic anhydride.  Hydroxythionaphthene - 7 - carboxylic acid is prepared by treating phenyl-1-thioglycollic-2-carboxylic acid dichloride with aluminium chloride in o-dichlorbenzene and steam-distilling the reaction mixture. 2,5-Dicarboxyphenylthioglycollic acid is prepared by diazotizing 2-aminoterephthalic acid, treating the diazo body with sodium polysulphide solution, reducing the disulphide derivative so obtained, and condensing the 2,5-dicarboxythiophenol with chloracetic acid.